CN113846423A - Preparation method of biological full-degradable composite fiber membrane - Google Patents
Preparation method of biological full-degradable composite fiber membrane Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention relates to a preparation method of a biological full-degradable composite fiber membrane, which adopts a first spinning solution and a second spinning solution to carry out conjugate electrostatic spinning to prepare the composite fiber membrane; the first spinning solution is obtained by dissolving a first polymer with ester groups in a first solvent, and the second spinning solution is obtained by dissolving a second polymer with hydroxyl groups in a second solvent; the first polymer and the second polymer are subjected to ester exchange reaction in the spinning forming process; the first polymer is polypropylene carbonate and/or chlorinated polyPropylene carbonate; the second polymer is more than one of polyoxyethylene, cellulose acetate and chitosan; the fiber diameter of the prepared fiber membrane is 500 nm-2.4 mu m, and the specific surface area of the fiber membrane is 53.49-197.33 m2(ii) in terms of/g. The invention improves the thermal stability, antibacterial property and adsorption property of PPC or C-PPC products by carrying out conjugated electrostatic spinning on the PPC and/or C-PPC polymer spinning solution containing nano silver particles and at least one polymer spinning solution of PEO, CA and CS.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and relates to a preparation method of a full-biodegradable composite fiber membrane.
Background
The medical dressing is used as a material for clinical wounds and is vital to wound care, and in recent years, novel materials combining multiple disciplines are applied to the medical dressing, and mainly comprise: films, polyurethane foams, hydrogel, alginate, etc. These novel dressings can provide a moist environment for the wound, and easily reveal and remove, can effectively promote wound healing, however, these novel dressings are mostly unable by biodegradable, and the cost of preparation is higher relatively, are not suitable for the environmental protection and energy saving theory of advocating at present.
In order to provide a novel biodegradable material with low preparation cost, the prior art proposes a biodegradable polymer material, namely Polypropylene carbonate (PPC), which is synthesized by taking carbon dioxide and propylene oxide as raw materials and has attracted extensive attention as a bidirectional environment-friendly material once coming out. PPC materials have wide application prospect in the fields of packaging materials, mulching films, adhesives, non-woven fabrics, medical materials and the like because of the advantages of complete biodegradation, good biocompatibility, no toxicity, capability of fixing carbon dioxide and the like.
However, the PPC material as an aliphatic carbonate has the characteristics of non-crystallinity, low glass transition temperature and the like, and has low thermal stability, antibacterial property and adsorptivity, so that the application range of the PPC material is greatly limited.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a preparation method of a fully biodegradable composite fiber membrane.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a biological full-degradable composite fiber membrane adopts a first spinning solution and a second spinning solution to carry out conjugate electrostatic spinning to prepare the composite fiber membrane; jets with opposite charges emitted from the two spinning nozzles in the electrospinning process are mutually attracted and held together in the stretching flight process, and finally the solvent is volatilized and solidified, and the positive charges and the negative charges are mutually offset and deposited on a receiving device;
the first spinning solution is obtained by dissolving a first polymer with ester groups in a first solvent, and the second spinning solution is obtained by dissolving a second polymer with hydroxyl groups in a second solvent;
the first polymer and the second polymer are subjected to ester exchange reaction in the spinning forming process;
in the invention, the first polymer and the second polymer are both biodegradable polymers, so the composite fiber membrane prepared by conjugated electrostatic spinning is also fully degradable;
the first polymer is polypropylene carbonate (PPC) and/or chlorinated polypropylene carbonate (C-PPC); the second polymer is more than one of polyethylene oxide (PEO), Cellulose Acetate (CA) and Chitosan (CS).
Taking the preparation of composite fiber membrane by PPC and PEO as an example, the reaction equation of the ester exchange of PPC and PEO in the conjugated electrostatic spinning process is as follows:
x1and y1Average degree of polymerization, x, of PPC and PEO, respectively1677 to 812, y12295 to 2456.
As a preferred technical scheme:
the preparation method of the fully biodegradable composite fiber membrane comprises the following specific steps:
(1) dissolving a first polymer in a first solvent to obtain a first spinning solution with the concentration of 8-15 wt%;
(2) dissolving a second polymer in a second solvent to obtain a second spinning solution with the concentration of 2-15 wt%;
(3) connecting the injector added with the first spinning solution to a positive voltage, connecting the injector added with the second spinning solution to a negative voltage, and performing conjugate electrostatic spinning to prepare the composite fiber membrane (namely, the first spinning solution and the second spinning solution simultaneously perform electrostatic spinning, jets with opposite charges emitted from two spinning nozzles in the electrospinning process attract each other in the stretching flight process to react, the solvent volatilizes, the composite fiber membrane is deposited on a receiving device, and the composite fiber membrane is obtained after the solvent volatilizes).
According to the preparation method of the fully biodegradable composite fiber membrane, the mass ratio of the first polymer in the first spinning solution to the second polymer in the second spinning solution is 1-15: 2; because the first polymer PPC or C-PPC of the invention is a two-way environmentally friendly material, i.e., the production source is CO causing greenhouse effect2The prepared polymer can be biodegraded, so that the composite fiber membrane of the invention is mainly PPC or C-PPC, and the content of the first polymer in the prepared composite fiber membrane is higher (most of the first polymer is higher, and is also higher by 1:1 and 1: 2).
The first spinning solution also contains nano Ag particles with the content of 0.01-2.0 wt% of the first polymer; because the composite fiber membrane is applied to medical dressings and the like, the content of the nano Ag particles is not easy to be too high, heavy metal poisoning can be caused by too high content of the nano Ag particles, and the sterilization effect is not obvious when the nano Ag particles are too low, so that the addition range is determined in the invention;
the average grain diameter of the nano Ag particles is less than or equal to 10 nm; too large diameter of the nano Ag particles can cause fiber fracture and destroy the continuity of the fibers, so that the diameter is not easy to be too large.
The preparation method of the fully biodegradable composite fiber membrane comprises the following process parameters in the step (3): the receiving distance is 10-50 cm, the receiving rotating speed is 20-200 rpm, and the translation speed is 10-500 mm/min; these are parameter ranges set by the effect of electrospinning process parameters on the performance and morphology of the fibrous membrane, within which the fibrous membrane produced has continuous and non-knotted fibers. For example, the receiving distance is related to the electric field intensity, and if the receiving distance is too large, the electric field intensity is too low, and the fiber cannot be dragged; too small a take-up distance can cause the fibers to break, resulting in discontinuity in the fibers produced. The other parameters are the same.
The receiving device adopted by the conjugate electrostatic spinning is a roller receiving device or a flat plate receiving device; the ambient temperature is 25 ℃ plus or minus 3 ℃, and the relative humidity is 35 plus or minus 5 percent. The temperature and humidity are set to control solvent volatilization, and the prepared fibers are discontinuous due to high temperature or low humidity and fast solvent volatilization; the prepared fiber is adhered due to low temperature or high humidity and slow solvent volatilization. Therefore, the range is controlled to be reasonable.
According to the preparation method of the fully biodegradable composite fiber membrane, the spinning speed of the first spinning solution is 0.03-0.09 mm/min, the inner diameter of a needle head adopted by a syringe added with the first spinning solution is 0.33-0.6 mm, and the positive voltage applied by the syringe added with the first spinning solution is 6-15 kV; these are parameter ranges set according to the influence of the electrospinning process parameters on the properties and morphology of the fibrous membrane.
According to the preparation method of the fully biodegradable composite fiber membrane, the spinning speed of the second spinning solution is 0.02-0.08 mm/min, the inner diameter of a needle head adopted by an injector added with the second spinning solution is 0.33-0.6 mm, and the negative voltage applied by the injector added with the second spinning solution is 4-12 kV; these are parameter ranges set according to the influence of the electrospinning process parameters on the properties and morphology of the fibrous membrane.
The preparation method of the fully biodegradable composite fiber membrane comprises the following steps of preparing a first solvent from dichloromethane and/or trichloromethane; the second solvent is more than one of water, N-dimethylacetamide, acetic acid and acetone; the principle of selecting the solvent is to prepare spinning solution with proper viscosity, which is suitable for electrostatic spinning, and the solvent type of the invention is determined by a large number of experiments.
The preparation method of the fully biodegradable composite fiber membrane comprises the steps of enabling the fiber diameter of the fully biodegradable composite fiber membrane to be 500 nm-2.4 mu m, and enabling the specific surface area of the fully biodegradable composite fiber membrane to be 53.49-197.33 m2In terms of/g (the specific surface area can be used to indirectly reflect the adsorption performance).
According to the preparation method of the fully biodegradable composite fiber membrane, the sterilization rate of the fully biodegradable composite fiber membrane to escherichia coli is 70% -98%.
The principle of the invention is as follows:
the invention relates to a conjugated electrostatic spinning, which is a spinning method that two spinning solutions are respectively connected with positive high voltage and negative high voltage, the spinning solutions with opposite charges are ejected from two spinnerets in the process of electrospinning and mutually attracted in the process of stretching and flying.
Meanwhile, when the fiber membrane is prepared by the electrospinning method, the diameter of the fiber membrane is related to many factors, such as polymer concentration (viscosity of spinning solution), voltage, inner diameter of a needle, spinning distance, receiving rate, spinning humidity and the like. According to the invention, the first polymer and the second polymer react in the conjugated electrostatic spinning process to produce new polyester, the new polyester has larger molecular weight, so that the properties of the spinning solution are changed, and the fiber membrane with thinner fiber diameter is prepared. The diameter of the fiber is reduced, the specific surface area is increased, and the adsorbability is improved.
Has the advantages that:
according to the preparation method of the fully biodegradable composite fiber membrane, the polymer spinning solution of at least one of PPC and/or C-PPC containing nano silver particles and the polymer spinning solution of at least one of PEO, CA and CS are subjected to conjugated electrostatic spinning together, so that the thermal stability, the antibacterial property and the adsorption property of the PPC and/or C-PPC product are improved, the application range of the PPC and/or C-PPC in medical dressings is further improved, the fully biodegradable composite fiber membrane has the fully biodegradable property, and the fully biodegradable composite fiber membrane is friendly to human health and environmental protection.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a PPC fiber membrane and a completely biodegradable composite fiber membrane (CA/PPC composite fiber membrane) prepared in example 2;
FIG. 2 is a thermogravimetric curve of a fully biodegradable composite fiber membrane (CA/PPC composite fiber membrane) prepared in example 2;
FIG. 3 is a thermogravimetric curve of the fully biodegradable composite fiber membrane (PEO/C-PPC composite fiber membrane) prepared in example 4;
FIG. 4 is an SEM photograph of a C-PPC fibrous membrane and a fully biodegradable composite fibrous membrane prepared in example 4 (PEO/C-PPC composite fibrous membrane); left: SEM of C-PPC fibrous membrane, right: SEM of PEO/C-PPC composite fiber membrane;
FIG. 5 is a thermogravimetric curve of a fully biodegradable composite fiber membrane (CA/C-PPC composite fiber membrane) prepared in example 5.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Silver nanoparticles used were provided by Hunion Corp, Korea, polypropylene carbonate PPC (maximum thermal decomposition temperature 208.55 ℃ C.), polypropylene carbonate C-PPC chloride (maximum thermal decomposition temperature 199.28 ℃ C.) were provided by applied chemistry research of Catharan, China academy of sciences, polyethylene oxide PEO (maximum thermal decomposition temperature 394.53 ℃ C.) was provided by Shanghai Michelin Biochemical technology Co., Ltd, cellulose acetate CA was provided by Sigma-Aldrich, and chitosan CS (maximum thermal decomposition temperature 362.48 ℃ C.) was provided by Kaisha chemical reagent Co., Ltd.
The molecular weight and molecular weight distribution of the starting material were as follows:
weight average molecular weight of polypropylene carbonate (PPC) is 6.9X 104The molecular weight distribution index is 1.2;
cellulose Acetate (CA) has a weight average molecular weight of 7.27X 104The molecular weight distribution index is 1.67;
weight average of chlorinated polypropylene carbonate (C-PPC)Molecular weight of 2.62X 105The molecular weight distribution index is 1.97;
polyethylene oxide (PEO) has a weight average molecular weight of 1.01X 105The molecular weight distribution index is 1.07;
the weight average molecular weight of Chitosan (CS) is 2.03X 105The molecular weight distribution index was 1.76.
The test method comprises the following steps:
specific surface area test method: the BET method is used in the invention, and is a method for measuring the specific surface area of the porous material commonly used at present.
The sterilization rate test method comprises the following steps: the invention is tested according to Japanese standard JISL1902-2002 'test method and antibacterial effect for textile antibacterial property'.
Example 1
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving PPC and nano Ag particles with the content of 0.02 wt% of the PPC (the average particle size of the nano Ag particles is 7.2 +/-2.3 nm) in dichloromethane to obtain a first spinning solution with the concentration of 9 wt%;
(2) dissolving PEO in water to obtain a second spinning solution with the concentration of 3 wt%; the mass ratio of PPC to PEO is 4: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.41mm, and the positive voltage applied by the injector added with the first spinning solution is 6 kV;
the spinning speed of the second spinning solution is 0.06mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.41mm, and the negative voltage applied by the injector added with the second spinning solution is 4 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 60rpm, and the translation speed is 300 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a roller receiving device; the ambient temperature was 25 ℃ and the relative humidity was 40%.
In the prepared biological full-degradable composite fiber membrane, the fiber diameter is 842 +/-109 nm; the weight average molecular weight of the biological full-degradable composite fiber membrane is 1.86 multiplied by 105Molecular weight distribution index of 2.98 and specific surface area of 104.28m2(ii)/g; the maximum thermal decomposition temperature of the fully biodegradable composite fiber membrane is 270.14 ℃, and the sterilization rate of the fully biodegradable composite fiber membrane to escherichia coli is 75%.
Example 2
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving PPC and nano Ag particles with the content of 0.12 wt% of the PPC (the average particle size of the nano Ag particles is 6.8 +/-2.7 nm) in dichloromethane to obtain a first spinning solution with the concentration of 12 wt%;
(2) dissolving CA in N, N-dimethylacetamide to obtain a second spinning solution with the concentration of 3 wt%; the mass ratio of PPC to CA is 7: 2;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.07mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.51mm, and the positive voltage applied by the injector added with the first spinning solution is 8 kV;
the spinning speed of the second spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.41mm, and the negative voltage applied by the injector added with the second spinning solution is 6 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 15cm, the receiving rotating speed is 80rpm, and the translation speed is 100 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a flat plate receiving device; the ambient temperature was 25 ℃ and the relative humidity was 35%.
Nuclear magnetic hydrogen spectrum and thermal weight loss curve of prepared biological full degradation composite fiber membrane (CA/PPC composite fiber membrane)As shown in fig. 1 and fig. 2, it can be seen from fig. 1 that the chemical shift of H in the PPC structure in the fully biodegradable composite fiber membrane is partially shifted, which proves that the PPC and CA in the fully biodegradable composite fiber membrane undergo a chemical reaction to cause a chemical shift deviation in the structure, and the analysis is performed according to the reaction principle: the PPC and CA are subjected to transesterification reaction, so that a polymer with larger molecular weight and more stable heat property is formed; the fiber diameter of the biological full-degradable composite fiber membrane is 1.41 +/-0.37 mu m, and the weight-average molecular weight of the biological full-degradable composite fiber membrane is 7.79 multiplied by 104(molecular weight it can be seen that the two polymers do transesterify during the conjugated electrospinning, the molecular weight increases, and the thermal stability increases), the molecular weight distribution index is 2.42, and the specific surface area is 68.75m2(ii)/g; as can be seen from fig. 2, the maximum thermal decomposition temperatures of the fully biodegradable composite fiber membrane were 280.39 ℃ and 344.30 ℃ (indicating that the fully biodegradable composite fiber membrane contains excess CA in addition to the polyester newly formed by the transesterification of PPC and CA), and the sterilization rate for escherichia coli was 75%.
Example 3
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving PPC and nano Ag particles with the content of 1.2 wt% of the PPC (the average particle size of the nano Ag particles is 4.7 +/-1.9 nm) in dichloromethane to obtain a first spinning solution with the concentration of 15 wt%;
(2) dissolving CS in a mixture of acetic acid and water in a mass ratio of 1:1 to obtain a second spinning solution with a concentration of 2.5 wt%; the mass ratio of PPC to CS is 6: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.09mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.6mm, and the positive voltage applied by the injector added with the first spinning solution is 10 kV;
the spinning speed of the second spinning solution is 0.09mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.33mm, and the negative voltage applied by the injector added with the second spinning solution is 10 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 100rpm, and the translation speed is 300 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a roller receiving device; the ambient temperature was 25 ℃ and the relative humidity was 40%.
In the prepared biological full-degradable composite fiber membrane, the fiber diameter is 872 +/-236 nm; the weight average molecular weight of the biological full-degradable composite fiber membrane is 2.65 multiplied by 105Molecular weight distribution index of 1.83 and specific surface area of 53.49m2(ii)/g; the maximum thermal decomposition temperature of the fully biodegradable composite fiber membrane is 248.41 ℃, and the sterilization rate of the fully biodegradable composite fiber membrane to escherichia coli is 84%.
Example 4
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving C-PPC and nano Ag particles with the content of 0.5 wt% of the C-PPC (the average particle size of the nano Ag particles is 5.6 +/-1.8 nm) in chloroform to obtain a first spinning solution with the concentration of 10 wt%;
(2) dissolving PEO in water to obtain a second spinning solution with the concentration of 3 wt%; the mass ratio of C-PPC to PEO is 4.4: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.41mm, and the positive voltage applied by the injector added with the first spinning solution is 12 kV;
the spinning speed of the second spinning solution is 0.06mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.41mm, and the negative voltage applied by the injector added with the second spinning solution is 4 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 60rpm, and the translation speed is 200 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a flat plate receiving device; the ambient temperature was 25 ℃ and the relative humidity was 40%.
The thermal weight loss curve and SEM of the prepared full-biodegradable composite fiber membrane are respectively shown in figures 3 and 4, and as can be seen from figure 4, the fiber diameter of the full-biodegradable composite fiber membrane is much smaller than that of the PPC fiber membrane, the fiber diameter of the full-biodegradable composite fiber membrane is 593 +/-175 nm, and the weight average molecular weight of the full-biodegradable composite fiber membrane is 3.27 multiplied by 105Molecular weight distribution index of 2.18 and specific surface area of 134.85m2Specific surface area per gram of C-PPC fibrous membrane (17.58 m)2The/g) is increased by more than 7 times, the contact area between the composite fiber membrane and a wound surface is increased when the composite fiber membrane is applied to medical dressing, and more tissue fluid and the like can be adsorbed, so that the adsorption performance of the prepared composite fiber membrane is enhanced; as can be seen from FIG. 3, the maximum thermal decomposition temperature of the fully biodegradable composite fiber membrane was 256.21 deg.C (indicating that only PEO and C-PPC in the fully biodegradable composite fiber membrane were newly formed into polyester by transesterification reaction without excessive PEO or C-PPC), and the sterilization rate against E.coli was 80%.
Example 5
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving C-PPC and nano Ag particles with the content of 0.5 wt% of the C-PPC (the average particle size of the nano Ag particles is 6.2 +/-3.1 nm) in dichloromethane to obtain a first spinning solution with the concentration of 12 wt%;
(2) dissolving CA in N, N-dimethylacetamide to obtain a second spinning solution with the concentration of 3 wt%; the mass ratio of C-PPC to CA is 4: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.41mm, and the positive voltage applied by the injector added with the first spinning solution is 12 kV;
the spinning speed of the second spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.41mm, and the negative voltage applied by the injector added with the second spinning solution is 6 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 80rpm, and the translation speed is 200 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a roller receiving device; the ambient temperature was 25 ℃ and the relative humidity was 35%.
The thermal weight loss curve of the prepared fully biodegradable composite fiber membrane is shown in FIG. 5, the fiber diameter of the fully biodegradable composite fiber membrane is 261 +/-109 nm, and the weight average molecular weight of the fully biodegradable composite fiber membrane is 2.77 multiplied by 105Molecular weight distribution index of 1.69 and specific surface area of 197.33m2(ii)/g; as can be seen from fig. 5, the maximum thermal decomposition temperatures of the fully biodegradable composite fiber membrane were 275.55 ℃ and 339.46 ℃ (indicating that the fully biodegradable composite fiber membrane contains excess CA in addition to the polyester newly formed by transesterification of CA and C-PPC), and the sterilization rate for escherichia coli was 90%.
Example 6
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving C-PPC and 0.5 wt% of nano Ag particles (the average particle diameter of the nano Ag particles is 6.4 +/-2.1 nm) with the content of the C-PPC in dichloromethane to obtain a first spinning solution with the concentration of 14 wt%;
(2) dissolving CS in a solution with a mass ratio of 1:1 to obtain a second spinning dope having a concentration of 2.5 wt%; the mass ratio of C-PPC to CS is 5.6: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.1mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.41mm, and the positive voltage applied by the injector added with the first spinning solution is 12 kV;
the spinning speed of the second spinning solution is 0.1mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.33mm, and the negative voltage applied by the injector added with the second spinning solution is 10 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 100rpm, and the translation speed is 400 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a flat plate receiving device; the ambient temperature was 25 ℃ and the relative humidity was 40%.
In the prepared biological full-degradable composite fiber membrane, the fiber diameter is 619 +/-294 nm, and the weight-average molecular weight of the biological full-degradable composite fiber membrane is 2.15 multiplied by 105Molecular weight distribution index of 2.81 and specific surface area of 178.54m2(ii)/g; the maximum thermal decomposition temperature of the biological full-degradable composite fiber membrane is 243.22 ℃, and the sterilization rate of the biological full-degradable composite fiber membrane to escherichia coli is 85%.
Example 7
A preparation method of a biological full-degradable composite fiber membrane comprises the following specific steps:
(1) dissolving a mixture of PPC and C-PPC in a mass ratio of 1:1 and nano Ag particles with the content of 1.5 wt% of the mixture (the average particle size of the nano Ag particles is 8.3 +/-1.7 nm) in dichloromethane to obtain a first spinning solution with the concentration of 12 wt%;
(2) dissolving CS in a mixture of acetic acid and water in a mass ratio of 1:1 to obtain a second spinning solution with a concentration of 3 wt%; the mass ratio of the mixture of PPC and C-PPC to CS is 5: 1;
(3) feeding the first spinning solution into a positive voltage-connected injector added with the first spinning solution, feeding the second spinning solution into a negative voltage-connected injector added with the second spinning solution, and then carrying out conjugated electrostatic spinning to prepare a composite fiber membrane;
the spinning speed of the first spinning solution is 0.1mm/min, the inner diameter of a needle head adopted by the injector added with the first spinning solution is 0.41mm, and the positive voltage applied by the injector added with the first spinning solution is 12 kV;
the spinning speed of the second spinning solution is 0.08mm/min, the inner diameter of a needle head adopted by the injector added with the second spinning solution is 0.33mm, and the negative voltage applied by the injector added with the second spinning solution is 10 kV;
the technological parameters of the conjugate electrostatic spinning are as follows: the receiving distance is 10cm, the receiving rotating speed is 100rpm, and the translation speed is 350 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a roller receiving device; the ambient temperature was 25 ℃ and the relative humidity was 40%.
In the prepared biological full-degradable composite fiber membrane, the fiber diameter of the biological full-degradable composite fiber membrane is 746 +/-312 nm, and the weight average molecular weight of the biological full-degradable composite fiber membrane is 2.68 multiplied by 105Molecular weight distribution index of 1.93 and specific surface area of 145.26m2(ii)/g; the maximum thermal decomposition temperature of the biological full-degradable composite fiber membrane is 237.85 ℃, and the sterilization rate of the biological full-degradable composite fiber membrane to escherichia coli is 90%.
Claims (9)
1. A preparation method of a biological full-degradable composite fiber membrane is characterized by comprising the following steps: carrying out conjugate electrostatic spinning by adopting a first spinning solution and a second spinning solution to prepare a composite fiber membrane;
the first spinning solution is obtained by dissolving a first polymer with ester groups in a first solvent, and the second spinning solution is obtained by dissolving a second polymer with hydroxyl groups in a second solvent;
the first polymer and the second polymer are subjected to ester exchange reaction in the spinning forming process;
the first polymer is polypropylene carbonate and/or chlorinated polypropylene carbonate; the second polymer is more than one of polyethylene oxide, cellulose acetate and chitosan.
2. The preparation method of the full biodegradable composite fiber membrane according to claim 1, which is characterized by comprising the following steps:
(1) dissolving a first polymer in a first solvent to obtain a first spinning solution with the concentration of 8-15 wt%;
(2) dissolving a second polymer in a second solvent to obtain a second spinning solution with the concentration of 2-15 wt%;
(3) and connecting the injector added with the first spinning solution to a positive voltage, and connecting the injector added with the second spinning solution to a negative voltage, and performing conjugated electrostatic spinning to prepare the composite fiber membrane.
3. The preparation method of the full biodegradable composite fiber membrane according to claim 2, wherein the mass ratio of the first polymer in the first spinning solution to the second polymer in the second spinning solution is 1-15: 2;
the first spinning solution also contains nano Ag particles with the content of 0.01-2.0 wt% of the first polymer;
the average grain diameter of the nano Ag particles is less than or equal to 10 nm.
4. The method for preparing the fully biodegradable composite fiber membrane according to claim 3, wherein the process parameters of the conjugate electrostatic spinning in the step (3) are as follows: the receiving distance is 10-50 cm, the receiving rotating speed is 20-200 rpm, and the translation speed is 10-500 mm/min;
the receiving device adopted by the conjugate electrostatic spinning is a roller receiving device or a flat plate receiving device; the ambient temperature is 25 ℃ plus or minus 3 ℃, and the relative humidity is 35 plus or minus 5 percent.
5. The method for preparing the biodegradable composite fiber membrane according to claim 4, wherein the spinning speed of the first spinning solution is 0.03-0.09 mm/min, the inner diameter of the needle of the syringe to which the first spinning solution is added is 0.33-0.6 mm, and the positive voltage applied to the syringe to which the first spinning solution is added is 6-15 kV.
6. The method for preparing the fully biodegradable composite fiber membrane according to claim 5, wherein the spinning speed of the second spinning solution is 0.02 to 0.08mm/min, the inner diameter of the needle of the syringe to which the second spinning solution is added is 0.33 to 0.6mm, and the negative voltage applied by the syringe to which the second spinning solution is added is 4 to 12 kV.
7. The method for preparing the fully biodegradable composite fiber membrane according to claim 6, wherein the first solvent is dichloromethane and/or trichloromethane; the second solvent is more than one of water, N-dimethylacetamide, acetic acid and acetone.
8. The method for preparing the fully biodegradable composite fiber membrane according to any one of claims 3 to 7, wherein the method comprises the following steps: the fiber diameter of the full biodegradable composite fiber membrane is 500 nm-2.4 mu m, and the specific surface area of the full biodegradable composite fiber membrane is 53.49-197.33 m2/g。
9. The method for preparing the fully biodegradable composite fiber membrane as claimed in claim 8, wherein the sterilization rate of the fully biodegradable composite fiber membrane to Escherichia coli is 70-98%.
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